Valorization of alum sludge via a pyrolysis platform using CO2 as reactive gas medium.

In an effort to seek a new technical platform for disposal of drinking water treatment sludge (DWTS: alum sludge), pyrolysis of DWTS was mainly investigated in this study. To establish a more sustainable thermolytic platform for DWTS, this study particularly employed CO2 as reactive gas medium. Thus, this study laid great emphasis on elucidating the mechanistic roles of CO2 during the thermolysis of DWTS. A series of the TGA tests of DWTS in CO2 in reference to N2 revealed no occurrence of the heterogeneous reaction between CO2 and the sample surface of DWTS. As such, at the temperature regime before initiating the Boudouard reaction (i.e., ≥700 °C), the mass decay patterns of DWTS in N2 and CO2 were nearly identical. However, the gaseous effluents from lab-scale pyrolysis of DWTS in CO2 in reference to N2 were different. In sum, the homogeneous reactions between CO2 and volatile matters (VMs) evolved from the thermolysis of DWTS led to the enhanced generation of CO. Also, CO2 suppressed dehydrogenation of VMs. Such the genuine mechanistic roles of CO2 in the thermolysis of DWTS subsequently led to the compositional modifications of the chemical species in pyrolytic oil. Furthermore, the biochar composite was obtained as byproduct of pyrolysis of DWTS. Considering that the high content of Al2O3 and Fe-species in the biochar composite imparts a strong affinity for As(V), the practical use of the biochar composite as a sorptive material for arsenic (V) was evaluated at the fundamental levels. This work reported that adsorption of As(V) onto the biochar composite followed the pseudo-second order model and the Freundlich isotherm model.

Valorization of sewage sludge via non-catalytic transesterification.

To seek a way to valorize sewage sludge (SS), it was chosen as a raw material for biodiesel production. As such, non-catalytic transesterification of dried SS was carried out, to enhance its value. Note that picking a waste material such as SS as an inexpensive lipid feedstock for biodiesel production, without lipid extraction, greatly increases the economic viability of biodiesel. Also, to enhance biodiesel sustainability, ethanol (EtOH) was employed as the acyl acceptor, in this study, and this was experimentally justified by results showing that employing EtOH as an acyl acceptor provided an effective means for compensating for the lower heating value arising from the large amount of palmitic (C16) acid in SS. This study experimentally proved that the fatty acid ethyl ester (FAEE) yield at 380 °C reached up to 13.33 wt% of dried SS. Given that the lipid content of dried SS is 14.01 ±â€¯0.64 wt%, the FAEE yield of 13.33 wt% implied that 95.14 wt% of lipid in dried SS had been converted into FAEEs. The introduced SS valorization in this study offered an excellent opportunity to address diverse environmental hazards arising from SS and associated emerging contaminants. Given that the optimal temperature for the non-catalytic conversion for biodiesel production from SS was found to be 380 °C, emerging contaminants, such as microplastics and antimicrobials, were simultaneously degraded, due to their inferior thermal stabilities. Lastly, considering that the introduced biodiesel conversion process is thermally induced, the SS reside after the biodiesel conversion process can be further used in thermo-chemical processes as raw materials for gasification and pyrolysis (future work).

Orange peel valorization by pyrolysis under the carbon dioxide environment.

To valorize biomass waste, pyrolysis of orange peel was mainly investigated as a case study. In an effort to establish a more sustainable thermolytic platform for orange peel, this study particularly employed CO2 as reactive gas medium. Accordingly, this study laid great emphasis on elucidating the mechanistic role of CO2 in pyrolysis of orange peel. The thermo-gravimetric analysis (TGA) confirmed that no occurrence of the heterogeneous reactions between the solid sample and CO2. However, the gaseous effluents from pyrolysis of orange peel experimentally proved that CO2 effectively suppressed dehydrogenation of volatile matters (VMs) evolved from the thermolysis of orange peel by random bond scissions. Moreover, CO2 reacted VMs, thereby resulting in the formation of CO. Note that the formation of CO was being initiated at temperatures ≥550 °C. The two identified roles of CO2 led to the compositional modification of pyrolytic oil by means of lowering aromaticity.

Biodiesel synthesis from fish waste via thermally-induced transesterification using clay as porous material.

The valorization of organic waste through biodiesel synthesis was investigated to explore the concept of hazardous waste-to-energy. Fish waste (mackerel waste) was chosen as a case study because of the growing concern regarding the treatment of food waste, which is potentially hazardous to the environment. This study focused on the thermally-induced transesterification of fish waste for the production of biodiesel (i.e., fatty acid methyl esters (FAMEs)). This process requires a porous material that allows for the collision between reactants (fish waste and methanol) to increase inside its pores at high temperatures. Therefore, commercial clay (montmorillonite) was used as the porous material in this study. The optimal temperature for the thermally-induced transesterification of unpurified mackerel oil was 380 °C, and the FAME recovery reached up to ˜72 wt.%. This study also proved that thermal cracking of polyunsaturated FAME species was initiated at temperatures ≥390 °C, and that fish waste is a promising feedstock for biodiesel when it is produced via thermally-induced transesterification over clay as a porous material.

CO2-mediated chicken manure biochar manipulation for biodiesel production.

This study employs chicken manure as a feedstock to produce different forms of energy to abate environmental burdens. To achieve ultimate carbon management, the possible utilization of CO2 during pyrolysis of chicken manure was fundamentally investigated. The roles of CO2 in pyrolysis of chicken manure include enhanced thermal cracking and shifting of the carbon distribution via reaction between volatile organic compounds and CO2. The identified roles induced by CO2 were catalytically enhanced because of the inorganic content in the feedstock. The morphology of biochar created from the chicken manure pyrolysis was significantly affected by CO2. For example, a well-developed pore structure was observed in the biochar developed under a CO2 environment; this biochar was used as an effective porous material for biodiesel synthesis.

Smart Food Waste Recycling Bin (S-FRB) to turn food waste into green energy resources.

Effective treatment of food waste is inherently difficult due to several factors, including its heterogeneous composition, high moisture content, and low heating value. To address these issues, this study aims to convert food waste into an energy resource using naturally occurring fermentative microorganisms embedded in wooden biochips (bio-catalysis), utilizing a "Smart Food Waste Recycling Bin" (S-FRB) system. High-throughput 16S rRNA gene sequencing analysis identified the major aerobic and facultatively anaerobic bacteria with alpha-diversity in terms of the Phylogenetic Diversity index ranging from 40.8 (initial stage) to 24.5 (mature stage), which indicates the microbial communities are relatively homogeneous and effective for use in the S-FBR. Operational results indicated that the organic content of food waste traded in the system increased from 53% up to 72% in the final end-product and achieved a mass reduction rate of approximately 80%. The heating value of the end-product, which was 3300 kcal/kg waste when measured by the differential scanning calorimeter (DSC) method, confirmed its high potential as a biofuel. Overall, the S-FRB system presents a practical approach for food waste treatment that solves the putrescible waste problem and maximizes utility through resource circulation.

Analysis of fatty acids in mouse tissue via in situ transmethylation with biochar.

Lipid derivatization technology-mediated fatty acid profiling studies have been suggested to dissect the contents of lipids in white fat and brown fat tissue. The focus of this study is to profile fatty acid lipidomics in brown adipose tissue and white adipose tissue of mice by derivatizing their lipids into fatty acid methyl esters via in situ transmethylation using a rice husk-derived biochar as porous media. The in situ transmethylation using biochar is advantageous in biological analysis because there was no loss of samples inevitably occurring in the loss of lipid in solvent extraction and purification steps.

Carbon dioxide assisted thermal decomposition of cattle excreta.

To develop the environmentally benign thermo-chemical process, this study placed great emphasis on the influence of CO2 on pyrolysis of cattle excreta for energy recovery. To this end, this study evaluates the possible enhanced energy recovery from cattle excreta using CO2 as reaction medium/feedstock in the thermal degradation of cattle excreta. The enhanced generation of CO in the presence of CO2 reached up to 15.15mol% (reference value: 0.369mol%) at 690°C, which was equivalent to ~4000 times more generation of CO. In addition to the enhanced generation of CO, the enhanced generation of H2 and CH4 in the thermal degradation of cattle excreta in CO2. Thus, the findings of this study revealed two genuine roles of CO2: 1) enhanced thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of cattle excreta and 2) direct reaction between VOCs and CO2 via gas phase reaction.

Quantification of volatile fatty acids from cattle manure via non-catalytic esterification for odour indication.

This report proposes a new approach to evaluate the odour nuisance of cattle manure samples from three different cattle breeds (i.e., native cattle, beef cattle, and milk cow) by means of quantification and speciation of volatile fatty acids (VFAs). To this end, non-catalytic esterification thermally induced in the presence of a porous material (silica) was undertaken, and the optimal operational parameters such as the derivatizing temperature (330°C) for the maximum yield (≥99±0.4%) of volatile fatty acid methyl esters (VFAMEs) were established. Among the VFA species in cattle manure based on quantification of VFAs, the major species were acetic, butyric and valeric acid. Considering the odour threshold of each VFA, our experimental results suggested that the major contributors to odour nuisance were C4-5 VFA species (i.e., butyric and valeric acid). Hydrothermal treatment was performed at 150°C for 0-40min to correlate the formation of VFAs with different types of cattle feed formulations. Our experimental data demonstrated that the formation of total VFAs is linearly proportional to the hydrothermal treatment duration and the total content of VFAs in native cattle, beef cattle, and milk cow manure samples reached up to ~1000, ~3200, and ~2800ppm, respectively. Thus, this study demonstrated that the degree of VFA formation is highly dependent on cattle feed formulations, which rely significantly on the protein content. Furthermore, the hydrothermal treatment provides a favourable condition for generating more VFAs. In this context, producing cattle manure into refused derived fuel (RDF) via a hydrothermal treatment is not a viable option to control odour.

Establishing a green platform for biodiesel synthesis via strategic utilization of biochar and dimethyl carbonate.

To establish a green platform for biodiesel production, this study mainly investigates pseudo-catalytic (non-catalytic) transesterification of olive oil. To this end, biochar from agricultural waste (maize residue) and dimethyl carbonate (DMC) as an acyl acceptor were used for pseudo-catalytic transesterification reaction. Reaction parameters (temperature and molar ratio of DMC to olive oil) were also optimized. The biodiesel yield reached up to 95.4% under the optimal operational conditions (380°C and molar ratio of DMC to olive oil (36:1)). The new sustainable environmentally benign biodiesel production introduced in this study is greener and faster than conventional transesterification reactions.

Quantification and speciation of volatile fatty acids in the aqueous phase.

This study lays great emphasis on establishing a reliable analytical platform to quantify and specify volatile fatty acids (VFAs) in the aqueous phase by derivatizing VFAs into their corresponding alkyl esters via thermally-induced rapid esterification (only 10 s reaction time). To this end, reaction conditions for the thermally-induced rapid esterification are optimized. A volumetric ratio of 0.5 at 400 °C for VFA/methanol is identified as the optimal reaction conditions to give ∼90% volatile fatty acid methyl ester (VFAME) yield. To maintain a high yield of VFAMEs, this study suggests that dilution of the sample to an optimum concentration (∼500 ppm for each VFA) is required. Derivatization of VFAs into VFAMEs via the thermally-induced rapid esterification is more reliable to quantify and specify VFAs in the aqueous phase than conventional colorimetric method.

Employing CO2 as reaction medium for in-situ suppression of the formation of benzene derivatives and polycyclic aromatic hydrocarbons during pyrolysis of simulated municipal solid waste.

This study proposes a strategic principle to enhance the thermal efficiency of pyrolysis of municipal solid waste (MSW). An environmentally sound energy recovery platform was established by suppressing the formation of harmful organic compounds evolved from pyrolysis of MSW. Using CO2 as reaction medium/feedstock, CO generation was enhanced through the following: 1) expediting the thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of the MSWs and 2) directly reacting VOCs with CO2. This particular influence of CO2 on pyrolysis of the MSWs also led to the in-situ mitigation of harmful organic compounds (e.g., benzene derivatives and polycyclic aromatic hydrocarbons (PAHs)) considering that CO2 acted as a carbon scavenger to block reaction pathways toward benzenes and PAHs in pyrolysis. To understand the fundamental influence of CO2, simulated MSWs (i.e., various ratios of biomass to polymer) were used to avoid any complexities arising from the heterogeneous matrix of MSW. All experimental findings in this study suggested the foreseeable environmental application of CO2 to energy recovery from MSW together with disposal of MSW.

Evaluating the effectiveness of various biochars as porous media for biodiesel synthesis via pseudo-catalytic transesterification.

This study focuses on investigating the optimized chemical composition of biochar used as porous material for biodiesel synthesis via pseudo-catalytic transesterification. To this end, six biochars from different sources were prepared and biodiesel yield obtained from pseudo-catalytic transesterification of waste cooking oil using six biochars were measured. Biodiesel yield and optimal reaction temperature for pseudo-catalytic transesterification were strongly dependent on the raw material of biochar. For example, biochar generated from maize residue exhibited the best performance, which yield was reached ∼90% at 300°C; however, the maximum biodiesel yield with pine cone biochar was 43% at 380°C. The maximum achievable yield of biodiesel was sensitive to the lignin content of biomass source of biochar but not sensitive to the cellulose and hemicellulose content. This study provides an insight for screening the most effective biochar as pseudo-catalytic porous material, thereby helping develop more sustainable and economically viable biodiesel synthesis process.

The effect of lead exposure on fatty acid composition in mouse brain analyzed using pseudo-catalytic derivatization.

We performed toxicological study of mice exposed to lead by quantifying fatty acids in brain of the mice. This study suggests that the introduced analytical method had an extremely high tolerance against impurities such as water and extractives; thus, it led to the enhanced resolution in visualizing the spectrum of fatty acid profiles in animal brain. Furthermore, one of the biggest technical advantages achieved in this study was the quantitation of fatty acid methyl ester profiles of mouse brain using a trace amount of sample (e.g., 100 µL mixture). Methanol was screened as the most effective extraction solvent for mouse brain. The behavioral test of the mice before and after lead exposure was conducted to see the effect of lead exposure on fatty acid composition of the mice' brain. The lead exposure led to changes in disease-related behavior of the mice. Also, the lead exposure induced significant alterations of fatty acid profile (C16:0, C 18:0, and C 18:1) in brain of the mice, implicated in pathology of psychiatric diseases. The alteration of fatty acid profile of brain of the mice suggests that the derivatizing technique can be applicable to most research fields associated with the environmental neurotoxins with better resolution in a short time, as compared to the current protocols for lipid analysis.

Estimating total lipid content of Camelina sativa via pyrolysis assisted in-situ transesterification with dimethyl carbonate.

Direct derivatization of C. sativa seed into FAMEs without lipid extraction was conducted for the quantification of lipid analysis via in-situ thermal methylation with dimethyl carbonate as an acyl acceptor on silica (SiO2). The introduced method had an extraordinarily high tolerance against impurities such as pyrolytic products and moisture. To ensure the technical completeness of in-situ methylation, thermal cracking of FAMEs transformed from C. sativa seed was also explored. Thermal cracking of unsaturated FAMEs such as C18:1, C18:2, C18:3 and C20:1 occurred at temperatures higher than 365°C due to their thermal instability. Thus, experimental findings in this study suggests not only that qualitative analysis of fatty acid profile in C. sativa seed via in-situ methylation using SiO2 could be achieve, but also that the total lipid content (42.65wt.%) in C. sativa seed could be accurately estimated.

In-situ pyrogenic production of biodiesel from swine fat.

In-situ production of fatty acid methyl esters from swine fat via thermally induced pseudo-catalytic transesterification on silica was investigated in this study. Instead of methanol, dimethyl carbonate (DMC) was used as acyl acceptor to achieve environmental benefits and economic viability. Thermo-gravimetric analysis of swine fat reveals that swine fat contains 19.57wt.% of water and impurities. Moreover, the fatty acid profiles obtained under various conditions (extracted swine oil+methanol+NaOH, extracted swine oil+DMC+pseudo-catalytic, and swine fat+DMC+pseudo-catalytic) were compared. These profiles were identical, showing that the introduced in-situ transesterification is technically feasible. This also suggests that in-situ pseudo-catalytic transesterification has a high tolerance against impurities. This study also shows that FAME yield via in-situ pseudo-catalytic transesterification of swine fat reached up to 97.2% at 380°C. Therefore, in-situ pseudo-catalytic transesterification can be applicable to biodiesel production of other oil-bearing biomass feedstocks.

A comparative study on per capita waste generation according to a waste collecting system in Korea.

As cities are becoming increasingly aware of problems related to conventional mobile collection systems, automated pipeline-based vacuum collection (AVAC) systems have been introduced in some densely populated urban areas. The reasons are that in addition to cost savings, AVAC systems can be efficient, hygienic, and environmentally friendly. Despite difficulties in making direct comparisons of municipal waste between a conventional mobile collection system and an AVAC system, it is meaningful to measure the quantities in each of these collection methods either in total or on a per capita generation of waste (PCGW, g/(day*capita)) basis. Thus, the aim of this study was to assess the difference in per capita generation of household waste according to the different waste collection methods in Korea. Observations on household waste show that there were considerable differences according to waste collection methods. The value of per capita generation of food waste (PCGF) indicates that a person in a city using AVAC produces 60 % of PCGF (109.58 g/(day*capita)), on average, compared with that of a truck system (173.10 g/(day*capita)) as well as 23 %p less moisture component than that with trucks. The value of per capita generation of general waste (PCGG) in a city with an AVAC system showed 147.73 g/(day*capita), which is 20 % less than that with trucks delivered (185 g/(day*capita)). However, general waste sampled from AVAC showed a 35 %p increased moisture content versus truck delivery.

Polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) mitigation in the pyrolysis process of waste tires using CO2 as a reaction medium.

Our work reported the CO2-assisted mitigation of PAHs and VOCs in the thermo-chemical process (i.e., pyrolysis). To investigate the pyrolysis of used tires to recover energy and chemical products, the experiments were conducted using a laboratory-scale batch-type reactor. In particular, to examine the influence of the CO2 in pyrolysis of a tire, the pyrolytic products including C1-5-hydrocarbons (HCs), volatile organic carbons (VOCs), and polycyclic aromatic hydrocarbons (PAHs) were evaluated qualitatively by gas chromatography (GC) with mass spectroscopy (MS) as well as with a thermal conductivity detector (TCD). The mass balance of the pyrolytic products under various pyrolytic conditions was established on the basis of their weight fractions of the pyrolytic products. Our experimental work experimentally validated that the amount of gaseous pyrolytic products increased when using CO2 as a pyrolysis medium, while substantially altering the production of pyrolytic oil in absolute content (7.3-17.2%) and in relative composition (including PAHs and VOCs). Thus, the co-feeding of CO2 in the pyrolysis process can be considered an environmentally benign and energy efficient process.